JP2020199437A - Method for manufacturing laminate having catalyst layer - Google Patents

Abstract

To provide a method for manufacturing a laminate in which a cured material layer of an adhesive or a seal material composed of a photocurable composition is formed with tight adhesion on a base material having a highly active catalyst layer.SOLUTION: A method for manufacturing a laminate having a catalyst layer is provided that includes the following steps 1 to 3: a step 1 of applying a photocurable composition onto a catalyst layer side of a base material having the catalyst layer; a step 2, namely, pre-curing step of within 1 minute after the step 1 and under atmosphere, irradiating the applied photocurable composition with light having peak wavelength of 350 to 420nm and with an irradiation amount of 20 to 1,000 mJ/cm2 emitted from an emission diode (hereinafter, referred to as "LED") having the light emission peak wavelength of 350 to 420nm; a step 3, namely, main curing step of using an LED having a light emission peak wavelength of 350 to 420nm or an ultraviolet irradiation device other than the LED thereby irradiating the photocurable composition pre-cured in the step 2, with light having a light emission peak wavelength of 350 to 420nm, at the peak wavelength of the LED or the ultraviolet irradiation device other than the LED with an irradiation amount of 50 mJ/cm2 or more under atmosphere with an oxygen concentration of 5% or less.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a laminate having a catalyst layer, and further, the laminate obtained from a substrate having a polymer electrolyte can be preferably used as a fuel cell, an electrochemical hydrogen pump, various sensors, and the like. , Belonging to these technical fields.

Due to growing interest in environmental and energy issues, there is a growing movement to popularize fuel cells as a power source for automobiles or households.
As a fuel cell, a polymer electrolyte fuel cell has advantages such as light weight and a low operating temperature, and is promising in terms of widespread use.
In a polymer electrolyte fuel cell, a power generation portion having catalyst layers (anode and cathode) on both sides of a polymer electrolyte membrane, and a gas supplied to the anode and a gas supplied to the cathode are separated or a flow path is formed. It is a laminate composed of a resin frame, a separator, and the like (for example, Patent Document 1).

The structure of the laminated body varies when viewed in detail, but in many cases, there is a portion for adhering two or more members constituting the laminated body. Further, a sealing material may be formed on the member and brought into contact with the other member through the sealing material to separate two types of fluids (gas or refrigerant) (for example, Patent Document 2). As described above, the polymer electrolyte fuel cell usually requires an adhesive and / or a sealing material.
When a polymer electrolyte fuel cell is put into practical use, it is usually necessary to stack a large number of cells, so that it is necessary to manufacture one cell in a short time. For this reason, short-time adhesion and short-time curing are required, and hot-melt adhesives (thermoplastic resins) are often used, but there are also proposal examples of photocurable compositions (for example, Patent Document 4, the same). 5). The advantages of the photocurable adhesive over the hot melt type adhesive are that it is easy to apply because it is liquid and that deformation of the adherend due to heat can be avoided. Further, the sealing material has an advantage that the curing time is overwhelmingly short as compared with the thermosetting type sealing material, and that the storage stability of the liquid is excellent.
Here, the adhesive or the sealing material may be arranged in contact with the catalyst layer (for example, Patent Documents 1 and 3).
Further, various studies and developments have been made on the catalyst layer in order to enhance the activity (for example, Patent Document 6).
The product form of the laminate having a catalyst layer is not limited to a fuel cell, and there are, for example, an electrochemical hydrogen pump (for example, Patent Document 7).

JP-A-2017-168364 JP-A-2009-158481 Japanese Unexamined Patent Publication No. 2014-999409 JP-A-2009-245797 International Publication No. 2018/190415 Pamphlet International Publication No. 2015/019953 Pamphlet JP-A-2017-226911

However, when the photocurable composition is applied onto the highly active catalyst layer and then irradiated with light to cure the composition, the adhesion may deteriorate.
An object of the present invention is to provide a method for producing a laminate in which a cured product layer of an adhesive or a sealing material made of a photocurable composition is formed with good adhesion on a base material having a highly active catalyst layer. That is.

As a result of diligent studies to solve the above problems, the present inventor has caused the decrease in adhesion between the base material having the catalyst layer and other base materials due to the low molecular weight (low molecular weight) contained in the photocurable composition. We have found that the cause is the decomposition of monomers such as meta) acrylates, and if we can provide means that can suppress the decomposition of the monomers, we will diligently study based on the idea that the above problems could be solved. It was.
As a result, after applying the photocurable composition on the substrate having the catalyst layer, it is promptly pre-cured using a light emitting diode (hereinafter referred to as "LED") with a relatively small irradiation amount. After that, it was found that the above-mentioned problem of deterioration of adhesion does not occur by irradiating the pre-cured composition in an environment with a low oxygen concentration with light to completely cure the composition, and completed the present invention.

The present invention relates to a method for producing a laminate having a catalyst layer including the following steps 1 to 3.
Step 1: Apply the photocurable composition to the catalyst layer side of the substrate having the catalyst layer Step 2: Within 1 minute after step 1, the emission peak wavelength is 350 to 420 nm in an air atmosphere. Pre-curing step of irradiating light with an irradiation amount of 20 to 1,000 mJ / cm ² at the peak wavelength of the LED possessed in Step 3: Oxygen concentration of 5% or less with respect to the photocurable composition pre-cured in step 2. In this atmosphere, an LED or an ultraviolet irradiation device other than an LED having a emission peak wavelength of 350 to 420 nm is used to irradiate light at an irradiation amount of 50 mJ / cm ² or more at the peak wavelength. Irradiation of the cured photocurable composition with an LED or an ultraviolet ray other than the LED having an emission peak wavelength of 350 to 420 nm in an atmosphere having an oxygen concentration of 5% or less.

According to the method for producing a laminate of the present invention, a laminate is produced on a substrate having a catalyst layer without reducing the adhesion of the cured product of an adhesive or a sealing material made of a photocurable composition. Can be the way.

The present invention relates to a method for producing a laminate having a catalyst layer including the following steps 1 to 3.
Step 1: Apply the photocurable composition to the catalyst layer side of the substrate having the catalyst layer Step 2: Within 1 minute after step 1, the emission peak wavelength is 350 to 420 nm in an air atmosphere. Pre-curing step 3: The photo-curing composition pre-cured in step 2 is irradiated with light at an irradiation amount of 20 to 1,000 mJ / cm ² at its peak wavelength, and the oxygen concentration is 5% or less. The main curing step of irradiating light with an LED or an ultraviolet irradiation device other than an LED having an emission peak wavelength of 350 to 420 nm at an irradiation amount of 50 mJ / cm ² or more at the peak wavelength. The material, the photocurable composition, and steps 1 to 3 will be described.
In the present specification, acrylate and / or methacrylate is referred to as (meth) acrylate, acryloyl group and / or methacryloyl group is referred to as (meth) acryloyl group, and acrylic acid and / or methacrylate is referred to as (meth) acrylic acid. , And a compound having one (meth) acryloyl group is referred to as a monofunctional (meth) acrylate, and a compound having two or more (meth) acryloyl groups is referred to as a polyfunctional (meth) acrylate.

1. 1. A base material having a catalyst layer A base material having a catalyst layer will be described.
Examples of the base material for forming the catalyst layer include polymer materials, carbon, metal oxides, sulfides and the like.
Examples of the polymer material include a hydrophilic polymer film and a hydrophobic polymer film.
Specific examples of the hydrophilic polymer film include a polyvinyl alcohol-based film and a cellulose ester-based film.
As the hydrophilic polymer film, an ion exchange resin (polymer electrolyte membrane) can also be used. Examples of the ion-exchange group in the ion-exchange resin include a sulfonic acid group, a carboxylic acid group, and a phosphonic acid group as the cation (cation) exchange group. Examples of the anion (anion) exchange group include an amino group, a quaternary ammonium group, a pyridyl group, an imidazole group, a quaternary pyridinium group, and a quaternary imidazolium group.
Specific examples of the ion-exchangeable resin include a polymer obtained by polymerizing an aromatic vinyl compound such as styrene, vinylpyridine, and vinylimidazole; a poly (meth) acrylic acid type; a perfluorosulfonic acid resin [for example, manufactured by DuPont]. Nafion (registered trademark)] and the like.

Specific examples of the hydrophobic polymer film include polycarbonate-based film, polyethylene terephthalate-based film, polyethylene naphthalate-based film, acrylic-based film, acrylic / styrene-based film, aliphatic polyamide (nylon) -based film, and aromatic polyamide-based film. , Polyarylate film, polyether sulfone film, polysulfone film, polyphenylsulfone film, polyether ether ketone film, polyphenylene oxide film, polyurethane film, polyimide film, ethylene-vinyl acetate copolymer system Examples thereof include films, polyvinyl chloride films, polyvinylidene chloride films, polyethylene films, polypropylene films, polycycloolefin films, polystyrene films, ABS films, and chlorinated polypropylene films.

Examples of carbon include carbon fibers, graphite, carbon nanotubes, fullerenes and the like that are heat-treated or compounded with a fluororesin or the like to form a sheet.

Metal oxides include silicon, aluminum, germanium, gallium, titanium, zirconium, vanadium, niobium, manganese, iron, cobalt, nickel, molybdenum, indium, tin, zinc, yttrium, tungsten, lantern, cerium, lithium, and sodium. Oxides such as, and composite oxides of these metals can be mentioned.

Examples of the sulfide include sulfides such as lithium, sodium, phosphorus, selenium, germanium, iron, zinc, and copper, and complexes thereof.

Examples of the catalyst layer formed on the above-mentioned substrate include metals, metal oxides, and metal complexes.
Examples of metals include platinum, palladium, ruthenium, rhodium, cobalt and the like.
These catalysts may be supported on a carrier such as carbon fine particles.
Further, in order to immobilize the catalyst or the carrier carrying the catalyst on a substrate such as a polymer film, a polymer binder is preferably used. As a polymer binder, Perfluo

The base material having a catalyst layer in the present invention is preferably applied to a polymer electrolyte (ion exchange resin) used in the manufacture of a fuel cell, an electrochemical hydrogen pump, various sensors, etc., in which the catalyst layer is formed. Can be done.
Specific examples of the polymer electrolyte in this case include a perfluorocarbon material having a sulfonic acid group. Commercially available polymer electrolytes include Nafion (registered trademark) manufactured by DuPont, Flemion FLEMION (registered trademark) manufactured by Asahi Glass Co., Ltd., Aciplex (registered trademark) manufactured by Asahi Kasei Corporation, and Gore Japan Co., Ltd. GORE-SELECT manufactured by GORE-SELECT (registered trademark) membrane and the like can be mentioned.
The polymer electrolyte may have a coating film formed on its surface, or may be a membrane / electrode assembly (MEA) for a fuel cell in which a polymer electrolyte membrane and an electrode are integrated. ..

2. 2. Photo-curable composition As the photo-curable composition used in the present invention, various compositions can be used as long as they contain (A) a photo-curable compound and (B) a polymerization initiator.

2-1. Component (A) In the present invention, the photocurable compound of the component (A) preferably contains a component (AR): a photoradical polymerizable compound.
Further, as the component (A), a so-called hybrid type composition can also be used in combination with the component (AR) and the component (AC); a photocationically polymerizable compound.
Hereinafter, the (AR) component and the (AC) component will be described.

2-1-1. (AR) component The (AR) component is a radically polymerizable compound.
Examples of the (AR) component include compounds having an ethylenically unsaturated group.
Specific examples of the compound having an ethylenically unsaturated component (AR) include a compound having a (meth) acryloyl group, a compound having a vinyl group, and the like, and a compound having a (meth) acryloyl group is preferable.
Further, as an example of the compound having a (meth) acryloyl group, the (AR1) component: a compound having one (meth) acryloyl group, and the (AR2) component: a compound having two or more (meth) acryloyl groups. Can be mentioned.

2-1-1-1. (AR1) component The (AR1) component is a compound having one (meth) acryloyl group.
Preferred compounds of the component (AR1) include alkyl (meth) acrylates, monofunctional (meth) acrylates having an alicyclic ring, and monofunctional (meth) acrylates having a hydroxyl group.

As the alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl ( Meta) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, etc. Can be mentioned.
Among these compounds, an alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms is preferable because it can increase the flexibility of the cured product of the composition and increase the peel strength against various materials.

A monofunctional (meth) acrylate having a hydroxyl group is preferable because the cured product of the composition has excellent adhesive strength with the polymer electrolyte.

Specific examples of the monofunctional (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , 2-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Examples thereof include acrylate, polytetramethylene glycol mono (meth) acrylate, and 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate.

The monofunctional (meth) acrylate having a ring structure enhances the toughness and heat resistance of the cured product of the composition, enhances the adhesive force with the polymer electrolyte and various materials, and enhances the resistance to immersion in hot water. It is preferable because it can be used.
Examples of the ring structure in the monofunctional (meth) acrylate having a ring structure include an alicyclic ring, an aromatic ring and a heterocycle.

Examples of the monofunctional (meth) acrylate having an alicyclic ring include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl ( Examples thereof include meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, and 1-adamantyl (meth) acrylate.
Examples of the monofunctional (meth) acrylate having an aromatic ring include benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of an alkylene oxide adduct of phenol, and (meth) acrylate of an alkylene oxide adduct of nonylphenol. Examples thereof include (meth) acrylate of an alkylene oxide adduct of phenoxyphenol, (meth) acrylate of an alkylene oxide adduct of p-cumylphenol, and (meth) acrylate of an alkylene oxide adduct of o-phenylphenol.
Examples of the monofunctional (meth) acrylate having a heterocycle include tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, and (2-methyl-2-ethyl-1,2, 3-Dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, N- (meth) acryloyloxyethyl hexahydrophthalimide, and Examples thereof include N- (meth) acryloyloxyethyl tetrahydrophthalimide.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the component (AR1), a compound other than the above can be used.
Specific examples thereof include n-butoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, 2,2,3,3-tetrafluoropropyl. (Meta) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl acid phosphate, acrylamide, N , N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acryloyl morpholine, N, N-dimethylaminopropyl ( Examples thereof include (meth) acrylamide and (3- (meth) acryloyloxypropyl) trimethoxysilane.

2-1-1-2. (AR2) component The (AR2) component is a compound having two or more (meth) acryloyl groups.
Specific examples of the compound having two (meth) acryloyl groups in the (AR2) component include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propane Di (meth) acrylates of aliphatic diols such as diol di (meth) acrylate and 1,9-nonane diol di (meth) acrylate;
Di (meth) acrylates of alicyclic diols such as cyclohexanedimethylol di (meth) acrylate and tricyclodecanedimethylol di (meth) acrylate;
Polyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate;
Esterification reaction products of neopentyl glycol, hydroxypivalic acid and (meth) acrylic acid;
Fluorene-based di (meth) acrylates such as 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene;
Di (meth) acrylate of alkylene oxide adduct of bisphenol compound such as di (meth) acrylate of bisphenol A alkylene oxide adduct;
Di (meth) acrylate of hydrogenated bisphenol A and other di (meth) acrylate of hydrogenated bisphenol compound;
It has two (meth) acryloyl groups in one molecule, such as an adduct of bisphenol A type epoxy resin and (meth) acrylic acid, and an adduct of 1,9-nonanediol diglycidyl ether and (meth) acrylic acid. Epoxy (meth) acrylate;
Polyester (meth) acrylates having two (meth) acryloyl groups in one molecule, such as esterifieds of phthalic acid, ethylene glycol and (meth) acrylic acid; and isophorone diisocyanates and 2-hydroxyethyl (meth) acrylates. Urethaneization reaction product, urethanization reaction product of tolylene diisocyanate, polyether diol and 2-hydroxypropyl (meth) acrylate, urethanization reaction product of hexamethylene diisocyanate, polyester diol and 2-hydroxybutyl (meth) acrylate , Urethane (meth) acrylate having two (meth) acryloyl groups in one molecule, such as a urethanization reaction product of isophorone diisocyanate, polycarbonate diol, and 4-hydroxybutyl (meth) acrylate.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Specific examples of the compound having three or more (meth) acryloyl groups in the (AR2) component include trimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, pentaerythritol di, tri or tetra (meth). ) Polyacrylate poly (meth) such as acrylate, dipentaerythritol penta or hexa (meth) acrylate, tri (meth) acrylate of isocyanurate ethylene oxide 3 mol adduct, glycerin tri (meth) acrylate, polyglycerin poly (meth) acrylate. Acrylate;
Tri (meth) acrylate of trimethylolpropane alkylene oxide adduct, tetra (meth) acrylate of trimethylolpropane alkylene oxide adduct, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, dipentaerythritol alkylene oxide adduct Poly (meth) acrylate of polyol alkylene oxide adduct such as penta or hexa (meth) acrylate, tri (meth) acrylate of glycerin alkylene oxide adduct, poly (meth) acrylate of polyglycerin alkylene oxide adduct;
Epoxy (meth) having three or more (meth) acryloyl groups in one molecule, such as phenol novolac type epoxy resin and (meth) acrylic acid adduct, cresol novolac type epoxy resin and (meth) acrylic acid adduct, etc. ) Acrylic;
Three or more in one molecule, such as the urethanization reaction product of isophorone diisocyanate and pentaerythritol tri (meth) acrylate, the isocyanurate-type trimer of hexamethylene diisocyanate and the urethanization reaction product of 4-hydroxybutyl acrylate. Urethane (meth) acrylate having (meth) acryloyl group;
Polyester (meth) acrylates having three or more (meth) acryloyl groups in one molecule, such as esterified products of phthalic acid, trimethylolpropane and (meth) acrylic acid, and dendrimer-type poly (meth) acrylates; A polymer obtained by adding glycidyl (meth) acrylate to a carboxylic acid of a (meth) acrylic polymer containing meth) acrylic acid as a constituent unit, or an epoxy group of a (meth) acrylic polymer containing glycidyl (meth) acrylate as a constituent unit. Examples thereof include polymers having a (meth) acryloyl group, such as a polymer obtained by adding (meth) acrylic acid to the polymer.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Further, as the (AR2) component, at least one skeleton selected from the group consisting of (AR2-1) polybutadiene, polyisoprene, hydrogenated polybutadiene, and hydrogenated polyisoprene (hereinafter referred to as "polydiene-based skeleton"). , And a compound having two or more (meth) acryloyl groups is preferable because it has excellent adhesiveness to various materials.

In the component (AR2-1), the molecular weight of the polydiene skeleton, that is, the molecular weight of the compound having the polydiene skeleton which is the raw material compound of the component (AR2-1), is a composition obtained with excellent solubility in the composition. The number average molecular weight (hereinafter referred to as “Mn”) is preferably 500 to 5,000, preferably 500 to 4,000, in terms of excellent adhesive strength and resistance to immersion in hot water. Is more preferable, and 700 to 3,000 is further preferable.
Examples of the compound having a polydiene skeleton include a polydiene skeleton and a compound having one or more hydroxyl groups [hereinafter referred to as "polydiene alcohol"], a compound having a polydiene skeleton and an epoxy group, a polydiene skeleton and a carboxyl group. Examples thereof include compounds having a polydiene skeleton and compounds having a carboxylic acid anhydride.
In the present invention, Mn (number average molecular weight) means a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) into polystyrene.
The molecular weight of the component (AR2-1) is preferably 1,000 to 100,000 in Mn, more preferably 3,000 to 80,000, and even more preferably 5,000 to 60,000. By setting the Mn of the component (AR2-1) to 1,000 or more, the cured product of the obtained composition has excellent adhesive strength and resistance to immersion in hot water, and by setting it to 100,000 or less, it can be applied to the composition. It can be excellent in solubility.
When the composition is used as a photocurable curable composition, the (meth) acryloyl group is preferably an acryloyl group because it has excellent curability of the composition.

Examples of the component (AR2-1) include the following components (AR2-1-1) to (AR2-1-6).
-Component (AR2-1-1): Polydiene alcohol, polyisocyanate, and urethanization reaction product of (meth) acrylate having a hydroxyl group.
-Component (AR2-1-2): Addition reaction product of a compound having an isocyanate group and a (meth) acryloyl group with respect to a polydiene alcohol.
-(AR2-1-3) component: (meth) acrylate of polydiene alcohol.
-Component (AR2-1-4): Adduct of (meth) acrylic acid to a compound having a polydiene skeleton and an epoxy group.
-Component (AR2-1-5): An adduct of (meth) acrylate having an epoxy group for a compound having a polydiene skeleton and a carboxyl group.
-Component (AR2-1-6): An adduct of (meth) acrylate having a hydroxyl group to a compound having a polydiene skeleton and a carboxylic acid anhydride.

As a method for producing the component (AR2-1-3), a polydiene alcohol and (meth) acrylic acid are subjected to a dehydration transesterification reaction under an acid catalyst, and a polydiene alcohol and a low molecular weight (meth) acrylate are esterified. Examples include a method of exchanging.

As the component (AR2-1), it is preferable to contain a compound having a urethane bond in the molecule (hereinafter, referred to as "polydiene urethane (meth) acrylate") from the viewpoint of excellent adhesive strength to various substrates.
As the polydiene urethane (meth) acrylate, the above-mentioned (AR2-1-1) component is preferable.
Further, among the components (AR2-1-1), urethane (meth) acrylate obtained by urethanizing a compound containing a polydiene diol, diisocyanate, and a hydroxyl group and a (meth) acryloyl group can be used with various substrates. It is particularly preferable because it has excellent adhesive strength.
Hereinafter, a compound containing polydienediol, diisocyanate, a hydroxyl group, and a (meth) acryloyl group, which are preferable raw material compounds of the (AR2-1-1) component, will be described.

Examples of the polydiene diol include polybutadiene diol, polyisoprene diol, and butadiene-styrene copolymer diol. Examples of the hydrogenated polydiene diol include hydrogenated polybutadiene diols, hydrogenated polyisoprene diols, and hydrogenated diols of butadiene-styrene copolymers.
The Mn of the polydienediol is preferably 500 to 5,000, more preferably 1,000 to 4,000. As described above, the polydiene diol satisfying the Mn has excellent solubility in the composition, and the cured product of the obtained composition has excellent adhesive strength and resistance to immersion in hot water.

Examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanates, hydrogenated tolylene diisocyanates, hydrogenated diphenylmethane diisocyanates, alicyclic diisocyanates such as hydrogenated xylylene diisocyanates, and tolylene diisocyanates, diphenylmethane diisocyanates, and trizine diisocyanates. , Naphthalene diisocyanate, aromatic diisocyanate such as xylylene diisocyanate, and the like.

Examples of the compound containing a hydroxyl group and a (meth) acryloyl group include caprolactones of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Modified products and glycidoldi (meth) acrylate and the like can be mentioned.
Among these compounds, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable.

As a preferable method for producing the component (AR2-1-1), a polydiene diol is reacted with a diisocyanate to produce a urethane prepolymer having an isocyanate group, and the prepolymer is reacted with a compound containing a hydroxyl group and a (meth) acryloyl group. Examples thereof include a method of reacting the compound (hereinafter referred to as “Production Method 1”) and a method of reacting a compound containing a polydiene diol, diisocyanate and a hydroxyl group and a (meth) acryloyl group (hereinafter referred to as “Production Method 2”).
In the present invention, the polydiene-based urethane (meth) acrylate obtained by the production method 1 has an easy molecular weight control, and the obtained polydiene-based urethane (meth) acrylate has excellent solubility in other components, and the obtained composition. Is preferable because it has excellent adhesive strength.

The molar ratio of the polydiene diol to the diisocyanate in the production of the preferred (AR2-1-1) component is preferably 1: 2.2 to 1: 1.05, preferably 1: 2 to 1: 1.1. Is more preferable, and 1: 1.8 to 1: 1.1 is even more preferable. In the (AR2-1-1) component reacted at this ratio, the obtained (AR2-1-1) component has excellent solubility in other (meth) acrylates, and the cured product of the obtained composition has adhesive strength. Will be excellent.

The content ratio of the component (AR2-1) is 20 to 100% by weight based on the entire component (AR) in that the cured product of the composition has excellent adhesiveness and resistance to immersion in hot water. It is preferably 20 to 94% by weight, more preferably 30 to 80% by weight.

2-1-1-3. As the other (AR) component, a compound having an unsaturated group other than the (meth) acryloyl group can be used.
For example, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactone, acryloylmorpholine and the like can be mentioned.
Further, when the composition of the present invention is used for a gas sensor, a fuel cell, etc., the volatile components of the composition are adsorbed on a metal such as a platinum catalyst existing on the surface of the polymer electrolyte, and the performance is deteriorated. In some cases. In order to solve this problem, it is preferable that the (AR) component does not contain volatile (meth) acrylate in an amount of 5% by weight or more based on the entire composition.
Examples of the volatile (meth) acrylate include (meth) acrylate having a molecular weight of 250 or less having no hydrogen-bonding group and (meth) acrylate having a molecular weight of 200 or less having a hydrogen-bonding group. Here, specific examples of the hydrogen-bonding group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an imide group, and an amide group.

2-1-2. (AC) component The (AC) component is a photocationically polymerizable compound.
Specific examples of the (AC) component include epoxy compounds, oxetane, vinyl ether and the like.
Hereinafter, these compounds will be described.

2-1-2-2-1. Epoxy compound The epoxy compound is not particularly limited as long as it has at least one epoxy group in the molecule, and various generally known curable epoxy compounds can be used. ..
Preferred epoxy compounds include a compound having at least two epoxy groups and at least one aromatic ring in the molecule (hereinafter referred to as "aromatic epoxy compound"), and at least two epoxy groups in the molecule. However, examples thereof include compounds in which at least one of them is formed between two adjacent carbon atoms constituting an alicyclic ring (hereinafter, referred to as "alicyclic epoxy compound").

Examples of the aromatic epoxy compound include bisphenol type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and brominated bisphenol A diglycidyl ether; phenol novolac type epoxy resin and cresol novolac type epoxy resin. Novolak type epoxy resin such as; In addition, biphenyl type epoxy resin, hydroquinone diglycidyl ether, resorcin diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, styrene-butadiene copolymer epoxidized product, styrene-isoprene Examples thereof include an epoxidized product of a polymer and an addition reaction product of a terminal carboxylic acid polybutadiene and a bisphenol A type epoxy resin.

Here, the epoxy resin refers to a compound or polymer having one or more epoxy groups in the molecule and cured by a reaction. According to conventions in the art, herein, a monomer may be referred to as an epoxy resin as long as it has one or more curable epoxy groups in the molecule.

Examples of the alicyclic epoxy compound include dicyclopentadiendioxide, limonendioxide, 4-vinylcyclohexendioxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and bis (3,4-epoxycyclohexyl). Examples thereof include compounds having at least one epoxidized cyclohexyl group such as methyl) adipate.

In addition to the above, aliphatic epoxy compounds such as 1,6-hexanediol diglycidyl ether, trimethylpropan triglycidyl ether, pentaerythritol tetraglycidyl ether, and polytetramethylene glycol diglycidyl ether; dihydric bisphenol A di An epoxy compound in which the aromatic ring is hydrogenated, such as glycidyl ether; a compound in which both ends of polybutadiene having both terminal hydroxyl groups are glycidyl etherized,
An internal epoxidized product of polybutadiene, a compound in which the double bond of the styrene-butadiene copolymer is partially epoxidized [for example, "Epofriend" manufactured by Daicel Chemical Industry Co., Ltd.], and an ethylene-butylene copolymer and poly. Examples thereof include polymer-based epoxy compounds such as compounds in which the isoprene unit of the block copolymer of isoprene is partially epoxidized.

As the epoxy compound, it is preferable to use a compound having a polydiene skeleton and an epoxy group [hereinafter, referred to as "(AC-1) component"].
The number of epoxy groups contained in one molecule is preferably two or more.

The content ratio of the component (AC-1) is 1 to 40% by weight, more preferably 1 to 30% by weight, still more preferably 1 to 25% by weight, based on the entire composition. By setting the blending amount of the component (B) to 1 to 40% by weight, the cured product of the composition has excellent adhesive strength to the polymer electrolyte and resistance to immersion in hot water.

Specific examples of the (AC-1) component include the following (AC-1-1) to (AC-1-4) components.
-(AC-1-1) component: A compound in which a double bond of polybutadiene or polyisoprene is epoxidized.
-(AC-1-2) component: A compound in which the double bond of polybutadiene or polyisoprene is epoxidized and hydrogen is added to the remaining double bond.
-Component (AC-1-3): An epoxy compound in which the hydroxyl groups of a high molecular weight compound having hydroxyl groups at both ends having a polydiene skeleton are glycidyl etherified with epichlorohydrin or the like.
-Component (AC-1-4): A compound obtained by adding a compound having two or more epoxy groups in one molecule to a carboxyl group of a high molecular weight body having a polydiene skeleton and having carboxyl groups at both ends.
As a more specific example of the component (AC-1-4), a compound obtained by adding a bisphenol A type epoxy resin to both terminal carboxyl group-modified polybutadiene can be mentioned.
Among these compounds, the component (AC-1) is preferable because the cured product of the composition has excellent resistance to immersion in hot water.

As the (AC-1) component, only one type may be used alone, or two or more types may be used in combination.
The molecular weight of the component (AC-1) is preferably 500 to 5,000 in Mn, and more preferably 500 to 3,000. By setting the Mn of the component (B) to 500 or more, the adhesive force with the polymer electrolyte can be enhanced, and by setting the Mn to 5,000 or less, the solubility in the composition can be improved. ..
The proportion of the epoxy group contained in the (AC-1) component is preferably 1 to 20%, more preferably 3 to 15% in terms of oxylan oxygen concentration. By setting the oxylane oxygen concentration of the component (B) in the range of 1 to 20%, the resistance to hot water immersion of the adhesive with the polymer electrolyte can be improved.
In the present invention, the oxylan oxygen concentration means a value measured according to ASTM D1652 (HBr titration).

2-1-2-2. Oxetane compound The oxetane compound is not particularly limited as long as it has at least one oxetane group in the molecule, and various compounds having an oxetane group can be used.
As the oxetane compound, a compound having one oxetane group in the molecule (hereinafter referred to as "monofunctional oxetane") and a compound having two or more oxetane groups in the molecule (hereinafter referred to as "polyfunctional oxetane") are preferable. Take as an example.

Examples of the monofunctional oxetane include an alkoxyalkyl group-containing monofunctional oxetane such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and an aromatic group-containing monofunctional oxetane such as 3-ethyl-3-phenoxymethyloxetane. A hydroxyl group-containing monofunctional oxetane such as 3-ethyl-3-hydroxymethyloxetane and the like are preferred examples.

Examples of the polyfunctional oxetane include the following compounds.
3-Ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane,
1,4-Bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene,
1,4-Bis [(3-ethyloxetane-3-yl) methoxy] benzene,
1,3-Bis [(3-ethyloxetane-3-yl) methoxy] benzene,
1,2-bis [(3-ethyloxetane-3-yl) methoxy] benzene,
4,4'-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl,
2,2'-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl,
3,3', 5,5'-tetramethyl-4,4'-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl,
2,7-Bis [(3-ethyloxetane-3-yl) methoxy] naphthalene,
Bis [4-{(3-ethyloxetane-3-yl) methoxy} phenyl] methane,
Bis [2-{(3-ethyloxetane-3-yl) methoxy} phenyl] methane,
2,2-Bis [4-{(3-ethyloxetane-3-yl) methoxy} phenyl] propane,
Ethereated modified product of novolak type phenol-formaldehyde resin with 3-chloromethyl-3-ethyloxetane,
3 (4), 8 (9) -bis [(3-ethyloxetane-3-yl) methoxymethyl] -tricyclo [5.2.1.0 ^2,6 ] decane,
2,3-Bis [(3-ethyloxetane-3-yl) methoxymethyl] norbornane,
1,1,1-Tris [(3-ethyloxetane-3-yl) methoxymethyl] propane,
1-butoxy-2,2-bis [(3-ethyloxetane-3-yl) methoxymethyl] butane,
1,2-Bis [{2- (3-ethyloxetane-3-yl) methoxy} ethylthio] ethane,
Bis [{4- (3-ethyloxetane-3-yl) methylthio} phenyl] sulfide,
1,6-bis [(3-ethyloxetane-3-yl) methoxy] -2,2,3,3,4,5,5-octafluorohexane,
3-[(3-Ethyloxetane-3-yl) methoxy] Hydrolyzed condensate of propyltriethoxysilane,
Tetrakis [(3-ethyloxetane-3-yl) methyl] silicate condensate, etc.

2-1-2-3. Vinyl ether As vinyl ether, for example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether , 2-Hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutylvinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl Vinyl ether, 1,6-hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol divinyl ether, m- Xylene glycol divinyl ether, o-xylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol divinyl ether, dipropylene glycol divinyl ether , Tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol divinyl ether, polypropylene glycol divinyl ether and the like, and derivatives thereof.

2-2. Component (B) Component (B) is a polymerization initiator, and it is preferable to use a radical polymerization initiator.
As the radical polymerization initiator, various radical generators can be used.
The content ratio of the component (B) is 0.1 to 15% by weight, preferably 0.2 to 13% by weight, and more preferably 0.5 to 10% by weight, based on the entire composition. If the content of the component (B) is less than 0.1% by weight, the curability of the composition is insufficient, and if it exceeds 15% by weight, the cured product of the composition deteriorates in terms of heat resistance, resistance to immersion in hot water, and the like.

As the component (B), a photoradical polymerization initiator that generates radicals by light (hereinafter referred to as “(b1) component”) and a radical polymerization initiator other than the component (b1) (hereinafter, “(b2) component”). ) Can be mentioned.
The composition used in the present invention is a photocurable composition containing the component (b1), but the component (b2) can also be used in combination.
Hereinafter, the component (b1) and the component (b2) will be described in order.

2-2-1. Component (b1) Component (b1) is a photoradical polymerization initiator, and various compounds can be used.

Specific examples of the component (b1) include benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl. ] -2-Hydroxy-2-methyl-1-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] propanone, 2-hydroxy-1-[ 4- [4- (2-Hydroxy-2-methyl-propionyl) benzyl] phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpho) Acetphenone compounds such as phosphorus-4-yl-phenyl) butane-1-one and 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole;
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenyl sulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and 4-methoxy-4' -Benzophenone compounds such as dimethylaminobenzophenone;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. Acylphosphine oxide compounds; as well as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2 -Il-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride, fluorothioxanthone and other thioxanthone compounds can be mentioned.
Examples of the compound other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, methyl phenylglioxyate, ethyl anthraquinone, phenanthrenequinone, camphorquinone and the like.

Among these compounds, the component (b1) preferably contains an acylphosphine oxide-based compound because the composition is excellent in curability.

When it is necessary to increase the thickness of the cured product, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured product, or when an ultraviolet absorber or pigment is used in combination. For the purpose of improving the curability of the composition, it is preferable to use a plurality of kinds of compounds selected from an acylphosphine oxide compound, a thioxanthone compound and an α-aminoalkylphenone compound in combination.
Preferred examples of the compound in this case include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and ethyl- (2,6-trimethylbenzoyl) as the acylphosphine oxide compound. 4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned. Examples of the thioxanthone compound include 2,4-diethylthioxanthone. , Isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc., and examples of the α-aminoalkylphenone compound include 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane. -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-) 4-Il-phenyl) -butane-1-one and the like can be mentioned.

As the component (b1), only one type may be used alone, or two or more types may be used in combination.

The content ratio of the component (b1) is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the entire component (B). By setting the ratio of the photoradical polymerization initiator to 0.1% by weight or more, the photocurability of the composition can be improved and the adhesion can be improved, and by setting it to 15% by weight or less, the composition can be cured. The internal curability of the object can be improved, and the adhesion to the substrate can be improved.

2-2-2. Component (b2) Component (b2) is a radical polymerization initiator other than component (b1), and a thermal radical polymerization initiator such as a peroxide or an azo compound can be used. A redox-based radical polymerization initiator can also be used.

Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1 , 1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoleperoxy) hexane, t-butylper Oxyisopropyl monocarbonate, t-butylperoxy2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2, 2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α '-Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthan hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, diisopropylbenzenehydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-Tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide and the like.
Specific examples of azo compounds include 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. , Azodi-t-octane, azodi-t-butane and the like.

As the component (b2), only one kind may be used alone, or two or more kinds may be used in combination. The organic peroxide can also be used as a redox initiator by combining with a reducing agent.

The content ratio of the component (b2) is preferably 10% by weight or less, preferably 5% by weight or less, based on the entire component (B), for the purpose of improving the curability of the composition and enhancing the adhesion to the substrate. More preferred. On the other hand, under the condition that the light reaches the composition sufficiently, it is preferable not to include it in consideration of the storage stability of the composition.

2-2-3. Other Component (B) When the component (AR) and the component (AC) are used in combination as the component (A) of the present invention, a photocationic polymerization initiator can be used as the component (B).
The photocationic polymerization initiator may be any compound that produces a cationic species or Lewis acid by irradiation with active energy rays. For example, an onium salt such as an aromatic diazonium salt, an aromatic iodonium salt and an aromatic sulfonium salt, and iron. -Allen complex and the like can be mentioned.

2-3. Other Ingredients As the composition used in step 1, in addition to the above-mentioned component (A) and component (B), various compounds can be blended as needed.
The composition used in step 1 contains the above-mentioned components (A) and (B) as essential components, but various other components can be blended depending on the purpose.

As the other component, it is preferable to include fine particles (hereinafter, referred to as "component (C)").
Hereinafter, the component (C) and other components other than the component (C) will be described.

2-3-1. Component (C) Component (C) is a fine particle.
Further, as the component (C), fine particles having a volume average primary particle diameter of 0.1 to 100 μm are preferable. By blending the component (C) having the particle size, the thickness of the adhesive layer can be kept above a certain level even when the polymer electrolyte and the other base material are bonded together and pressure is applied. In addition, screen printability is also improved.

As the component (C), those that do not dissolve in the components (A) to (C) are preferable.
Specific examples of the component (C) include inorganic fine particles and polymer fine particles.
Examples of the inorganic fine particles include alumina, silica, and zirconia.
Examples of the polymer fine particles include chemically crosslinked polymer fine particles and non-crosslinked polymer fine particles that are insoluble in the components (A) to (C). Examples of the non-crosslinked polymer fine particles include polyolefins, fluorinated polyolefins, and cellulosic resins.

As the component (C), only one type may be used alone, or two or more types may be used in combination.

Among these, as the component (C), it is preferable that the component (C) contains polymer fine particles because of its excellent dispersibility and stability, and it is more preferable that the component (C) contains chemically crosslinked polymer fine particles. preferable.

Specific examples of the chemically crosslinked polymer fine particles include acrylic fine particles containing a polymerization unit of a (meth) acrylate monomer such as methyl methacrylate, polyurethane fine particles, and the like.
As a method for cross-linking acrylic fine particles, a method of copolymerizing a monomer mixture containing a monofunctional (meth) acrylate monomer and a bifunctional (meth) acrylate monomer, or a method of copolymerizing a monofunctional (meth) acrylate monomer and an alkoxysilyl. Examples thereof include a method in which a monomer mixture containing a (meth) acrylate monomer having a group is copolymerized, and an alkoxysilyl group is hydrolyzed and condensed to crosslink.

The volume average primary particle size of the component (C) is preferably 0.1 to 100 μm, more preferably 0.2 to 70 μm, still more preferably 0.5 to 50 μm, and particularly preferably 0.5 to 30 μm.
The volume average primary particle diameter of the component (C) means a value measured by a laser diffraction / scattering type particle size distribution meter (wet method).

When the component (C) is blended in the composition of the present invention, the content ratio thereof is preferably 1 to 60% by weight, more preferably 5 to 50% by weight, based on the entire composition. ..

2-3-2. Other components other than the component (C) As the other components other than the component (C), particles in the particle size range not included in the component (C) (for example, particles having an average primary particle size of less than 0.1 μm of several tens of nm to several nm). Fine particles), polymers other than the components (A) and (C) (hereinafter referred to as "other polymers"), tackifiers, plasticizers, defoamers, leveling agents, polymerization inhibitors, stabilizers, organic solvents, etc. Can be mentioned.

As the fine particles in the particle size range not included in the component (C), fine particles (fumes) having an average primary particle size of less than 0.1 μm and several tens of nm to several nm, which can be used for the purpose of imparting thixophilicity at the time of coating. (Dosilica, etc.), and particles having a particle diameter of several hundred μm to several mm, which can be used for the purpose of considerably increasing the thickness of the cured product or reducing the curing shrinkage rate.

Specific examples of other polymers include uncrosslinked polymers having solubility in the composition.
Examples of the polymer include (meth) acrylic resin, polystyrene, styrene-acrylonitrile copolymer, polybutadiene, polyisoprene, polyisobutylene, hydrogenated polybutadiene, hydrogenated polyisoprene, maleated polybutadiene, maleated polyisoprene, and maleized. Polypropylene, chlorinated polypropylene, petroleum resin, hydrogenated petroleum resin, xylene resin, polytetramethylene glycol, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-acrylic copolymer, polyester, polyamide, polyurethane, polycarbonate, etc. Can be mentioned.
These may act as an adhesion-imparting component, or may act as a tackifier or a plasticizer, which will be described later.

Specific examples of the tackifier include rosin ester and petroleum resin.
Specific examples of the plasticizer include dioctyl phthalate and the like.
Examples of the defoaming agent include hydrocarbon-based, silicone-based, fluorosilicone-based, fluorine-based, mineral spirits-based, and the like, and known ones can be used.
Examples of the leveling agent include hydrocarbon-based, silicone-based, and fluorine-based agents, and known ones can be used.

Examples of the polymerization inhibitor include hydroquinone and methoxyhydroquinone, and known ones can be used.
Examples of the stabilizer include hindered phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, hindered amine-based antioxidants, ultraviolet absorbers, and the like, and known ones can be used.

As the organic solvent, known ones can be used as long as they dissolve the components (A) and (B). However, considering that the solvent drying step lowers the production efficiency and there is a concern about residual solvent, it is preferable not to add an organic solvent.

2-4. Method for Producing Composition The composition used in the present invention contains the above-mentioned components (A) and (B), and the method for producing the composition may be in accordance with a conventional method, and the above-mentioned (A) and (B). It can be produced by mixing the components, further mixing the other components if necessary, and stirring according to a conventional method.
In this case, it can be heated as needed.

The viscosity of the composition used in the present invention shall be appropriately set by those skilled in the art according to the coating method in order to obtain a coated surface having excellent coatability, that is, smoothness, which can be used in the manufacturing process of the laminate. Can be done.

3. 3. Process 1
Step 1 relates to a step of applying a photocurable composition to the catalyst layer side of a base material having a catalyst layer.
The base material having the catalyst layer and the photocurable composition are as described in detail above.
The coating method will be described below.

3-1. Coating method In step 1, the photocurable composition is coated on the catalyst layer side of the base material having the catalyst layer.
The coating method may be appropriately set according to the composition to be used and the purpose. For example, various coating methods such as dispenser, screen printing, roll coater, inkjet, spray, and electrostatic attraction coating are adopted. be able to.

In this case, the film thickness of the coated composition may be appropriately set according to the substrate having the catalyst layer to be used and the application, and is preferably 10 to 500 μm, more preferably 20 to 100 μm.

3-2. Other Steps In the present invention, after coating the composition, a light-transmitting member may be attached to the coated surface. In this case, the light-transmitting member is adhered in a later curing step and integrated with the base material having the catalyst layer.

4. Process 2
In step 2, within 1 minute after step 1, light is irradiated at the peak wavelength of 20 to 1,000 mJ / cm ² by an LED having an emission peak wavelength of 350 to 420 nm in an air atmosphere. This is a pre-curing process.

As the LED light source, as long as it has an emission peak wavelength of 350 to 420 nm, only one type may be used, or two or more types may be used in combination.
For example, a 365 nm LED and a 405 nm LED may be combined. In this case, the sum of the irradiation amounts of each wavelength is adjusted so as to be within the target range.
The irradiation amount varies depending on the thickness of the coating film, the illuminance, and the like, but may be appropriately set according to the emission wavelength and the compounding composition of the LED light source.

The time from the coating in step 1 to the irradiation with light shall be within 1 minute.
Further, it is preferably within 1 minute and 50 seconds after coating, more preferably within 30 seconds, and particularly preferably within 10 seconds.
By shortening this time, the decomposition amount can be reduced as much as possible even when the catalyst decomposes the low molecular weight (meth) acrylate at a very high rate.

When a dispenser is adopted as the coating method in step 1, it is preferable that the LED light source has a structure in which the LED light source tracks immediately behind the nozzle portion of the dispenser. As a result, the time from coating to pre-curing can be shortened to less than 1 second.

In step 2, light is irradiated at the peak wavelength of the LED at an irradiation amount of 20 to 1,000 mJ / cm ² . If it is out of this range, the effect of the present invention of exhibiting good adhesion even on a highly active catalyst layer becomes small, which is not preferable.
Specifically, if it is less than 20 mJ / cm ² , the effect of pre-curing is almost lost and the adhesion is lowered. On the contrary, if it exceeds 1,000 mJ / cm ² , most of the component (B) is decomposed. It disappears, and in the main curing in step 3, the active species of the component (B) are almost eliminated, so that the curing does not proceed.

5. Process 3
In step 3, the photocurable composition pre-cured in step 2 is peaked by an LED or an ultraviolet irradiation device other than LED having an emission peak wavelength of 350 to 420 nm in an atmosphere of an oxygen concentration of 5% or less. This is the main curing step of irradiating light with an irradiation amount of 50 mJ / cm ² or more at a wavelength.

In step 3, the oxygen concentration is irradiated with light in an atmosphere of 5% or less.
If the oxygen concentration is greater than 5%, the amount of residual monomers increases, and the residual monomers may be decomposed by the catalyst after the heat resistance test, resulting in a decrease in adhesion. The oxygen concentration is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less, and particularly preferably 0.5% or less.
The lower limit of the oxygen concentration is not particularly specified from the viewpoint of the performance of the obtained laminate, but is preferably 0.001% or more from the viewpoint of manufacturing cost.

As a method for setting the oxygen concentration to 5% or less, it is preferable to use an inert gas having an oxygen concentration of less than 5%. Examples of the inert gas include nitrogen, carbon dioxide, water vapor, argon and the like, and nitrogen is preferable.
When nitrogen gas is used, from the viewpoint of economy, nitrogen gas having a purity of about 96 to 99% obtained by membrane separation of air can be used, and for the purpose of reducing the oxygen concentration in a short time, , Nitrogen gas having a purity of 99% or more can also be used.

As a method of reducing the oxygen concentration around the photocurable composition pre-cured in step 2 to 5% or less, a method of covering the entire member and allowing an inert gas to flow into the member, an oxygen concentration of less than 5%. Examples thereof include a method of transferring to a space by a conveyor or the like, and a method of spraying an inert gas having an oxygen concentration of less than 5% onto a pre-cured photocurable composition.

The LED light source having an emission peak wavelength of 350 to 420 nm may be appropriately selected depending on the situation in which it is used. For example, when a light-transmitting member is bonded and bonded, and the member absorbs ultraviolet rays, it is preferable to select, for example, an LED having a diameter of 405 nm. In that case, it is necessary to use a photocurable resin that is sensitive to light of 405 nm. On the other hand, when bonding members that transmit light with a wavelength of 350 nm or more, or when using a photocurable resin like a sealing material or adhesive (when directly exposed to a light source), UV-LED curing is widely used. The 365 nm or 385 nm UV-LED used can be preferably used.

In this curing step, an ultraviolet irradiation device other than the LED, such as a high-pressure mercury lamp or a metal halide lamp, can be used, but the LED is preferable in terms of reducing damage to the catalyst layer.

In step 3, light is irradiated at an irradiation amount of 50 mJ / cm ² or more at the peak wavelength of the light source. When it is less than 50 mJ / cm ² , even if the oxygen concentration is reduced, the residual monomer is not sufficiently reduced, and the adhesion to the catalyst layer may be lowered.

6. Uses of Laminates The laminates obtained in the present invention can be used for various purposes.
A preferable laminate is a laminate containing a polymer electrolyte as a base material having a catalyst layer. The structure of the laminate is a laminate composed of a substrate, a cured product formed from the above composition, and the other substrate, and both or one of the substrate and the other substrate is used. , Polymer electrolyte.
The polymer electrolyte is preferably a perfluorocarbon material having a sulfonic acid group from the viewpoint of being chemically stable.

Applications of the obtained laminate include polymer electrolyte fuel cells, electrochemical hydrogen pumps, actuators used for medical purposes, and various sensors such as medical sensors and gas sensors.

The present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.
In the following, "parts" means parts by weight, and the numerical value indicating the blending ratio in the table means% by weight.

1. 1. Manufacturing example
1) Preparation of electrolyte membrane-catalyst layer laminate
(1) Platinum catalyst-supported carbon (platinum-supported amount 46 wt%, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., TEC10E50E) in 30 ml of concentrated sulfuric acid having a sulfonated purity of 96 wt% and 30 ml of fuming sulfuric acid having an SO ₃ content of 25 vol%. Was immersed and sulfonated by stirring at a liquid temperature of 40 ° C. for 8 hours. This was filtered, immersed in 4 L of ion-exchanged water at 70 ° C., stirred for 30 minutes, and subjected to a washing step of filtering again to remove unreacted sulfuric acid and fuming sulfuric acid. This washing step was repeated until the washing water became neutral. After washing, it was dried in air at 60 ° C. overnight and then pulverized in a mortar to obtain a sulfonate catalyst.

(2) Preparation of Transfer Sheet for Catalyst Layer Formation 1-butanol 10 g, 3-butanol 10 g, ionomer dispersion liquid [Nafion (registered trademark) D2020, manufactured by DuPont, polymer content 20 wt%] 5 g in addition to the above-mentioned sulfonated catalyst 2 g. And 21 g of water were added, and the mixture was stirred and mixed with a disperser to prepare a paste composition for forming a catalyst layer. Next, this composition was applied onto a PET film so that the platinum weight after drying the catalyst layer was 0.4 mg / cm ^2, and dried to prepare a transfer sheet for forming a catalyst layer.

(3) Preparation of Electrolyte Membrane-Catalyst Layer Laminated Two sheets of the above-mentioned transfer sheet for forming a catalyst layer cut into a size of 70 mm × 30 mm were prepared, and a polymer electrolyte membrane (Nafion) cut into a size of 75 mm × 35 mm was prepared. The catalyst layer was placed on both sides of NRE-212 (registered trademark) NRE-212, DuPont, 0.002 inch thick) so that the catalyst layer faced the electrolyte membrane side, and hot-pressed at 135 ° C., 5.0 MPa, and 150 seconds. After that, the PET film was peeled off to prepare an electrolyte membrane-catalyst layer laminate. This is hereinafter referred to as "catalyst layer base material A".

2) Preparation of photocurable composition
(1) Synthesis of urethane acrylate GI-1000 (hydroxyl value 68.7 mgKOH / g, Mn about 1,) manufactured by Nippon Soda Co., Ltd. as hydrogenated polybutadiene having hydroxyl groups at both ends in a 2 L four-mouth separable flask. 500) 900 g (1.1 mol as a hydroxyl group), 0.65 g of 2,6-di-t-butyl-p-cresol, and 244 g of isophorone diisocyanate (2.2 mol as an isocyanate group) are charged, and a stirrer is attached to stir and mix. And dissolved. A thermometer, a gas introduction pipe, a dropping funnel, and a cooling pipe were attached to this flask, and a mixed gas of oxygen and nitrogen (oxygen 5%) was circulated. To this solution, 0.013 g of ferric Narsem as a catalyst was added to dissolve the solution, and then the solution temperature was raised to 80 ° C. for 5 hours, followed by 158 g of 4-hydroxybutyl acrylate (1.1 mol as a hydroxyl group). ) Was charged and reacted for 5 hours to synthesize urethane acrylate. This is hereinafter referred to as "UA-1".

(2) Preparation of photocurable composition 50 g of the above-mentioned UA-1, 50 g of acrylate [Aronix M-111 manufactured by Toa Synthetic Co., Ltd.] with 1 mol of nonylphenol EO, and Speed Cure TPO, which is a photoradical polymerization initiator. 2 g of [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by Rambuson Co., Ltd.] and 0.1 g of BYK-1790 [Big Chemie Japan Co., Ltd.] as an antifoaming agent were blended at 60 ° C. It was dissolved by stirring.
Next, 50 g of acrylic crosslinked fine particles [MX-500 manufactured by Soken Kagaku Co., Ltd.] having an average particle size of 5 μm were added and dispersed by a planetary stirrer to prepare a photocurable composition.
This is hereinafter referred to as "photocurable composition A".

2. 2. Example
1) Example 1 (Method for manufacturing a laminate having a catalyst layer)
(1) Step 1
On the catalyst layer base material A, the photocurable composition A was applied by screen printing to a width of 6 mm, a length of 60 mm, and a thickness of 0.05 mm.

(2) Step 2
Ten seconds after coating, pre-curing was performed by irradiating with 250 mJ / cm ² ultraviolet rays using a 365 nm LED.
As the LED, a controller 8332A manufactured by CCS Inc. and a standard head 8361 were used, and an LED having a line lens AC8343 attached to the tip of the head was used (the irradiation range becomes a rectangle of 5 mm × 16 mm). This LED head is set above the speed-adjustable movable stage so that the stage crosses the short direction of the irradiation range, and the irradiation amount is 250 mJ / cm ^{2 in} advance when the stage speed is 6 mm / sec. It was adjusted. At this time, the illuminance in the central portion of the irradiation range was 500 mW / cm ² . In this way, by screen-printing immediately next to the pre-adjusted LED and stage, the time from screen-printing to pre-curing can be shortened to 10 seconds.

(3) Step 3
A cycloolefin polymer film [ZF14 manufactured by Nippon Zeon Corporation] having a width of 10 mm and a length of 60 mm, which had been previously corona-treated, was placed on the pre-cured coating film to a width of 6 mm and a length of the pre-cured coating film. It was bonded so that 30 mm was adhered.
Next, put this in a stainless steel container equipped with quartz glass on the upper surface, a gas inlet with a cock on the side surface, a gas outlet with a cock, and an oxygen sensor, and replace with nitrogen for 5 minutes to adjust the oxygen concentration in the container. After setting the volume to 0.1 vol%, the container is sealed, and the UV-LED irradiation device (365 nm) manufactured by Centec Co., Ltd. equipped with a stage moving device is irradiated with 1,000 mJ / cm ² ultraviolet rays to perform main curing, and the catalyst is used. A laminated body having layers was prepared (peak illuminance 200 mW / cm ² , stage speed 8 mm / sec, 2 passes at 500 mJ / cm ² per pass).

2) Example 2
In the pre-curing of step 2 of Example 1, a laminate was produced in the same manner as in Example 1 except that the moving speed of the LED head was 15 mm / sec and the ultraviolet irradiation amount was 100 mJ / cm ² .

3) Example 3
The laminate was produced in the same manner as in Example 1 except that the pre-curing of Step 2 of Example 1 was carried out twice in succession and the ultraviolet irradiation amount in the pre-curing was 500 mJ / cm ² .

4) Comparative Example 1
A laminate was produced in the same manner as in Example 1 except that the time from application to pre-curing was changed to 2 minutes in Example 1.

5) Comparative example 2
In Example 1, a laminate was produced in the same manner as in Example 1 except that the pre-curing in step 2 was omitted.

6) Comparative example 3
In the pre-curing of step 2 of Example 1, a laminate was produced in the same manner as in Example 1 except that the moving speed of the LED head was set to 150 mm / sec and the ultraviolet irradiation amount was changed to 10 mJ / cm ² .

7) Comparative example 4
The laminate was produced in the same manner as in Example 1 except that the pre-curing of Step 2 of Example 1 was carried out eight times in succession and the ultraviolet irradiation amount in the pre-curing was changed to 2,000 mJ / cm ² . ..

8) Comparative example 5
A laminate was produced in the same manner as in Example 1 except that the oxygen concentration at the time of main curing was changed to 6% in Example 1.

9) Comparative example 6
A laminate was produced in the same manner as in Example 1 except that the main curing condition was set to 1 pass at a conveyor speed of 160 mm / sec and the ultraviolet irradiation amount was changed to 25 mJ / cm ² .

10) Comparative Example 7
A laminate was produced in the same manner as in Example 1 except that the main curing was omitted in Example 1.

3. 3. After the laminate after the main curing in the adhesion evaluation step 3 of the photocurable composition layer on the catalyst layer was left at room temperature under air for 1 hour, it was put into a drying oven at 120 ° C. for 10 minutes and then taken out to be a cured film. The appearance of the was visually observed. From the results, the adhesion was evaluated at the following four levels.
The results are shown in Table 1 together with the experimental conditions.
〇: No peeled part Δ: Slight peeling was observed at the edge of the cured product ×: The edge of the cured product was peeled by about 1 mm from the catalyst layer × ×: Most of the cured product was peeled from the catalyst layer

4) Evaluation Results As is clear from the results of Examples 1 to 3, the laminate obtained by the production method of the present invention was excellent in adhesion.
On the other hand, the manufacturing method of Comparative Example 1 in which the time from step 1 to step 2 exceeds 1 minute, the manufacturing method of Comparative Example 2 in which the second step was not carried out, and the lower limit of the irradiation amount of 20 mJ in the second step. In the production method of Comparative Example 3 in which the amount was less than / cm ² , the adhesion of the obtained laminate was insufficient, and slight peeling was observed at the end of the cured product.
Further, the production method of Comparative Example 4 in which the upper limit of the irradiation amount in the second step of 1,000 mJ / cm ² was exceeded, the production method of Comparative Example 5 in which the upper limit of the oxygen concentration in the third step exceeded 5%, and the third step. In the production method of Comparative Example 6 in which the lower limit of the irradiation amount of 50 mJ / cm ² was not satisfied, the adhesion of the obtained laminate was lowered, and peeling of about 1 mm occurred from the catalyst layer at the end of the cured product. It was.
Further, in the production method of Comparative Example 7 in which the third step was not carried out, the adhesion of the obtained laminate was greatly reduced, and most of the cured product was peeled off from the catalyst layer.

The production method of the present invention can be preferably applied to the production method of a laminate having a catalyst layer.
In particular, a laminate obtained from a base material having a polymer electrolyte is preferably used as a fuel cell, an electrochemical hydrogen pump, various sensors, and the like.

Claims (4)

A method for producing a laminate having a catalyst layer, which comprises the following steps 1 to 3.
Step 1: Apply the photocurable composition to the catalyst layer side of the base material having the catalyst layer Step 2: Within 1 minute after step 1, the emission peak wavelength is 350 to 420 nm in an air atmosphere. Pre-curing step 3: Pre-cured photocurable composition in step 2: Light is irradiated with a light emitting diode (hereinafter referred to as "LED") having an irradiation amount of 20 to 1,000 mJ / cm ² at its peak wavelength. On the other hand, in an atmosphere with an oxygen concentration of 5% or less, an LED or an ultraviolet irradiation device other than the LED having a emission peak wavelength of 350 to 420 nm irradiates light at the peak wavelength at an irradiation amount of 50 mJ / cm ² or more. Curing process The method for producing a laminate according to claim 1, further comprising a step of laminating a light-transmitting member on the coated photocurable composition in the step 1. The method for producing a laminate according to claim 1, which comprises a step of laminating a light-transmitting member on a pre-cured photocurable composition after performing the step 2. The method for producing a laminate according to any one of claims 1 to 3, wherein the photocurable composition contains (meth) acrylate.